Arylalkylacylformamidines



- formulas, Ar, R, and R are defined above.

, Typical starting formamidinium salts that are reacted with the amides are the following: r

, LN,N-diphenyl-N,N'-dimethylforrriamidinium fluoborate, N,N'-diphenyl-N,N'-diethylformamidinium' fluoborate,-

r 3,164,633 ARYLALKYLACYLFORMAMIDINES David I-Il Clemens, Willow Grove, Pa., assignor to Rohm- & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing.

Filed d. 19, 1961,-Ser. No. 146,3s7 Claims; (21. 260- -558) This invention relates to a'rylalkylacylformamidines of in which R is an aliphatic hydrocarbon group, such as alkyl,R is an aryl or alkyl group, and Ar is an aromatic hydrocarbon group, such as an aryl group. The alkyl group which: R and RR may represent may be straight or branched and include-the. cycloalkyl group. Typical alkyl groups are methyl,ethyl,"1isopropyl, butyl, 2-ethylhexyl, and the like. When R is an aryl group, it preferably represents a phenyl or -naphthyl group. Ar-pre f eri ably representsan aryl group, such asgphenyl oranaphthyl. Typical of the.new.-arylalkylacylformamidines of the inventionare,the' following:- f l. f: N-phenyl-N me'thyl-N berizoylformamidine, N-phenyl-N-ethyl-N'-benzoylformamidine,

' jN phenyl-N-methyl-N-butyrylformamidine, N-phenyl:N-methyl-N'-isobutyrylformamidine,j

N-phenyl-N-butyl-N'-benzoylforrnamidine,f

' like- The invention provides a method for. preparing the arylalkylacylformamidines which comprisesreactinga formamidinium salt'of the formula 1 Bar]. B,

V with an amide of the formula C( 2 in the presence. of an alkali metal hydride.

N,N'-diphenyl-N,N'-dipropylformamidinium fiuoborate;

N,N'-di hen l-N,N'-di-t-but IfOrmamidinium fluoborate, p y y a and their equivalents'are substituted. weight unless indicated to the contrary.

l and borate. W

Typical amides, which are reacted-with the -formarni-i dinium salts, are the following; .,benzamide, propanarnide,'; 'butyramide, acetamide, and the l=ike., j

3,164,633 rPatentad Jan, 5, 1965 ICC In the -reaction ..between the alliali metal salt oi the amide, or of the amidein the presence of an alkali metal hydride, and the formamid-inium salt, it is preferred to employ one mole of each of the reactants to insure completeness of the reaction. However, there mayfalso be used'an excess of the amide, such as two orthr'e'e moles of the amide for each mole of the formamidinium salt.

The reaction between the formamidinium salt and the amide may becarriedout over a broad range of temperatures, such 'as in the range of 10 to 150 C. and

short of the decomposition temperature of the formamir invention may be conveniently carried out the presence of an inert solvent. For this purpose, there may be employed hydrocarbon solvents, such as benzene, toluene,

dine product s. Advantageously, the reaction is carried outin the temperature range of to 35 C. The

progress'of the reaction may be followed bythe disappearance of the formamidinium salts. The process of the Xylene; a chlorinated hydrocarbon, such as ethylene dichloride; ethers, such-as 1,2-din 1ethoxyethane, diethylene f, glycol, dimethylether, tetraethylene glycol dimethyl,

ether, dibutylle'ther, tetrahydrofuran, dioxane, dim'ethyl;

ether, and theflike.

f The product, when insoluble in the reaction mixture, may be separated by filh'atio'nand it may befurther purified 'by washing with wate'riand suitable solvents, such as N-o-tolyidyl-N-methyl-N-benzo lforrnamidine, and V the tebyjcrystalilzanon' i H acetone. If the product is more soluble in-the reaction .mixture, it maybe isolated by-adding a water-immiscible solvent, followed by extraction by .Water, removal of the solvent, as by distillation under useful'as the active ingredients of pesticidal compositions,

particularly asfungicides-and herbicides." in standard fungicidal tests, they are toxic to Alterrra'ridsol'ani, 5

Moniliniaf frli'ctiwlz'a, and Stemp'hyliunr sarcinaeforme.

, As a herbicide, the arylalkylacylformamidines are toxic to yvild oats, mustard, and millet: In agricultural ap- 1' plications, the compounds of the invention may be formed in the form of dusts orpowders, one ormore of the alkylacylformamidine's being taken up on a finely divided solid carrier, .such as'talc. Also, solutions of the form- 'In the above,

of 1,2-dimeth0Xymethane andthe're 'is added 1.75 parts j l of a 53% dispersion of sodium hydride in mineral'oil.

- In theformamidinium salt, the a ion, an, ma hem,

Placed by o her anions, suchl s bromine, iodi 50 andthe like." l

"The alkali metal hydride, MI-l, which may beusediis a hydride in which M is an alkali" metalrof anatomic alkaligrnetal salt of the amide definedaabove. Accordthe presence of the metal hydride.

e, or by preparing it in 'situ ".ingly, the method-may be'carried out by: preforming the v alkali metal salt of the amid (by the use .of'the amid amidines'in Water-miscible solvents may be prepared.

Optionally, emulsifyingagents ean be added to the liquid.-

to provide self-emulsifying"concentrates for preparation of aqueous sprays. 1 g g V The following examples are provided to further illustrate the invention. They are not to be construed as a limitation thereon. :It will. be apparent to one skilled in Itheart that'the manipulative steps will generally be substantially identical when equivalent portions of reactants I Example 1(a) There is dissolved 4.6 parts of benzamide in parts Th e mixture is heated to 80," Quntil evolution o fhydrogen gas ceases. There is thenadde'd 12 parts of N,N'-

diphenyl-N,N-dimethylformamidinium fluoborate. The

mixture is allowed to stand oyernight with stirring andis filtered. Thefiltrate is evaporated to yielda solid' which crystallizes from ether to give 4.2 parts of N-phenyl- N-methyl N'-benzoylformamidine. melting point of;62 to'65 and analyzes at: 75.08%

carb'on'(theoretical 75.60%), 5.97% hydrogen (theoretiv cal and 11.64% nitrogen (theoretical 11.76% Example 1 1)) n fu'lvalen t portion of hydride.

reduced pressure, and

All partsfare by e I The product has a to) fis repeated substituting sodium. hydride A "borate The the formula V 7 Example 2 Example l 1(a) N,N diphenyl-N,N'-di-nhuty1formamidinium fluoborate for the N,N'-dipheny1-N,N"-dimethylformamidinium fluoproduct is N pheny l-N-n -butyl-N'-benzoy1- formamidine. 1

r v Ex anzpl ei iq) e Example 1(a) V is repe ated substituting 2.2 pa'rtsiof V acetam idef for the benzamide. T The product is -N.-pheny1- N-niethfikl-N'-acetylformamidine.

' i V V 1 Example3( b) f a *Pmrw is repeated substituting for the acetamide an equivalent portion of the amidefoiibehenic acid, The" product is N-phenyl N-methyl N(-eicqsanylformamidine. This application is"a, continuation in-part of United States application Serial No. 145,736, filed October 1211961.

Y 1 J I, claim; i

1. e "A methhd comprisesreacting a -jaikeli metal salt of an'amide of for prepari g 'a combouhdof the formula;

V M I i j with at formamidihiilmsaltof the formula is repeatedfsilbstituting 15 amat 'i phenyl substituent V y is sodium. 1

in which R andiAr a reid efi ried above jaildin whichv the alkali metal salt has an atomic number "of 3 to 55.

2. The process of claim 1, in which R is a phenyl group, R is' a methyl group, and-Ar is a phenyl group. 3. The process of claim 1, which A'r is a nitro- 4. The process of claim 5. The methodof claim 1, in which the alkali metal salt of the amide is prepared insitu'byreacting the amide with the for mamidi ium salt ofthe-foi muls. c

1 in which R is 1a lower alkyl group; R? is selected from the group consisting of; a lowei alkyl and ,phenyl, and

V isan aryl substittient selected from the gr oup consist mg of; to1\ 1idyl, phenyl, haphthyl tand itrophenyl which i in th ipiesence' of an alkali meteilj hydride, s which the alkailime tai has an" atomic number of 3 to 55.

' Refer ez cesi Cited iri the filefof this ieteht FOREIGN PATENTS France Lin w ic the alkeilim'etal Apt. 19,1939 

1. A METHOD FOR PREPARING A COMPOUND OF THE FORMULA 